Dispersant compositions and toxicant concentrates containing the same



United States Patent DIsPERs'ANT COMPOSITIONS AND TOXICANT CONCENTRATES CONTAINING THE SAME No Drawing. Filed Aug. 27, 1956, Ser. No. 606,182

27 Claims. (Cl. 167-42) My invention relates to the production of new and useful dispersant compositions .and to liquid biocidal toxicant compositions, particularly in the form of toxicant concentrates, containing said dispersants.

It has been found to be highly desirable, in certain situations, to be able to apply to an earth soil, in which plant or vegetable life is grown or contemplated to be grown, both water-soluble fertilizer material and also a desired pesticide, to wit, Water-insoluble organic solventsoluble insecticide or soil fumigant, hereafter generically called biocidal toxicant, in the form of a single composition. Efforts to provide such a composition, for instance, in the form of a stable, mobile, pourable or pumpable liquid emulsion, by simple mixing, present certain serious problems. The water-soluble fertilizer materials comprise water-soluble compounds, typical examples of which are potassium chloride, potassium nitrate, ammonium nitrate, ammonium sulphate, potassium sulphate, ammonium phosphate, and urea, with or without supplemental materials.

When dissolved in water to form strong solutions, particularly solutions approximating concentrated solutions, constituting the aqueous phase, and admixed with biocidal toxicant concentrates containing biocidal toxicants dissolved in organic solvents and insoluble in said aqueous phase, or solutions of such biocidal toxicants in organic solvents wherein said latter solutions, constituting the oleaginous phase, are insoluble in said aqueous phase, unstable dispersions form which readily and promptly separate out in the form of layers. Efforts to emulsify such aqueous phases and such oleaginous phases by means of usual types of emulsifying agents used in the toxicant emulsion field have proved entirely unsatisfactory. Non-ionic emulsifiers of the type of the polyoxyethylene derivatives of lipophillic materials, for instance,

polyethylene glycol ethers of sorbitan monosterate, polyethylene glycol ethers of sorbitan monooleate, alkyl phenoxy polyoxyethanols, iso-octyl phenol polyoxyethylene ethers, and the like, have been found 'to be in effective since they are salted out by the strong electrolytes in the high concentrations used in liquid fertilizer solutions. Similarly, higher alkyl a'ryl sulfonates, such as alkali metal, ammonium, magnesium or calcium salts U of dodecyl benzene sulfonate, and the like, have likewise.

been found to be entirely unsatisfactory, whether used in conjunction with the non-ionic emulsifiers of thetype mentioned above or by themselves.

The problem of providing satisfactory emulsions of aqueous liquid fertilizer solutions, particularly strong solutions, containing upwards of 20% of water-soluble fertilizer ingredients such as the monovalent and polyvalent ionic compounds described above and up to saturated aqueous solutions of said fertilizer solutions, with water-insoluble organic solvent-soluble biocidal toxicants Patented Mar. 21, 19 61 compositions, but these must be prepared immediately prior to being used and must be used promptly since, among other things, their stability is of extremely short duration. Other special combination 'of ingredients have been suggested, for instance, which are of use in liquid fertilizer-biocidal toxicant compositions but only if the liquid fertilizer contains trivalent phosphate ions and urea. In the presence of monovalent ions such as chlorides or nitrates, such latter compositions are of no commercial value because the emulsifying action of the combination of ingredients is destroyed.

I have discovered new and useful biocidal toxicant concentrates (and dispersant compositions for use therein) which, when admixed, by simple mixing, with liquid fertilizer compositions in the form of strong aqueous solutions, say in excess of 20% concentration up to saturation, produce homogeneous emulsions or dispersions which remain usable for periods of the order of at least several hours. My invention makes it unnecessary to pre-mix the biocidal toxicant concentrate with water just prior to admixing it with the liquid fertilizer solution, as is required with certain heretofore known biocidal toxicant concentrates. All that is necessary, in the case of biocidal toxicant concentrates made in accord ance with my invention, is simple mixing or agitation with the liquid fertilzer solution. Moreover, my novel biocidal toxicant concentrates can effectively be used with liquid fertilizer compositions irrespective of whether the latter contain monovalent or polyvalent ions, and they are also usable with more dilute solutions of liquid fertilizers as, for instance, those containing of the order of 10 to 15% of solids. Thus, they have a universality of utility which is a most important practical consideration. i

and which may be characterized as an alcohol non-tertiary (that is, primary or secondary) amine, a reactive hydrogen of an amino group of said amine being replaced by a fatty acid acyl radical containing at least 8 and especially from 12 to 18 carbon atoms, and a reactive hydrogen of an hydroxy group of said amine being replaced by an acyl radical of a sulfopolycarboxylic acid radical, for instance, the sulfosuccinic acid radical -OCCHCH2COOM OaM' wherein M is an alkali metal or an organic substituted ammonium radical, and M is an organic substituted ammonium radical.

At least most of the compounds encompassed by said (a) ingredient may further be subdivided into two groups,

corresponding to the following formula where RCO is a fatty acyl radical containing at least 8 and especially from 12 to 18 carbon atoms, X is the ,cornpletely deaminated and dehydroxylated residue of has, so far as -I am aware, not remotely been solved despite intensive efforts to do so. In certain instances,

by means of special combinations of ingredients, it has- I V metal or an organic substituted ammonium radical, M"

been possible to prepare liquid fertilizer-biocidal toxicant analcohol primary or secondary amine, especially monoethanolamine and monoisopropanol'amine, Y is the completely decarboxylated residue of a polycarboxylicacid, especially an aliphatic dicarboxylic acid, M is an alkali is an organic substituted ammonium radical, and n is 1 or 2.

The acyl radical (RCO-) of said (a) ingredient is derived from oils or fats, hydrogenatedor not, such as 'a,s7o,20a i l 1 propylamine, triisopropylamine, and commercial mixtures "of said isopropylamines; butyl amine; amyl amine; monoisopropanolamine, diisopropanolamine, triisopropanol'amine and commercial mixtures of said isoprococonut oil, babassu oil, corn oil, castor oil, linseed oil, 5 panolamines; ethanolamines such as monoethanolamine, fish oils, cottonseed oil, soya bean oil, palm nut kernel diethanolamine, triethauolamine, and commercial mixoil, and the like, or fatty acids such as lauric acid, myristic turcs thereof; polyamines such as aminoethyl ethanolacid, palmitic acid, stearic acid, oleic acid, linoleic acid amine, ethylenediamine, diethylenetriamine, hydroxyethyl and commercial mixtures of such fatty acids predominant ethylenediamine, and hexamcthylenediamine; hcxylaminc; in content of a desired one or ones of said fatty acid, or cyclohexylamine; dimethylbenzylamine, benzylamine; acylating derivatives of such acids as, for example, the morpholine; methylcyclohexylamine; alkyl alkanolamines acyl chlorides thereof. such as ethyl diethanolamine and diethyl ethanolamine;

The alcohol primary and secondary amines, particufurfurylamine; piperidine; 2-ami no-2-methyl-l-propanol; larly water-soluble hydroxy-alkyl primary amines, which Z-amino-l-butanol; methyl piperidine, and the like, and are utilized to form the higher fatty acid amide linkage compatible mixtures of any two or more thereof. 4 in the molecule in the preparation of the (a) ingredient In the case of said first or (a) ingredient, it will be 1 can be selected from a large group, typical or illustraseen that, in the case of sulfodicarboxylic acid ester detive examples of which are monoethanolamine, monorivatives, the said salt may be the organic substituted propanolamiue,diethanolamine,isopropanolamine, monoammonium di-salt, that is, where both M and M are butanolamine, isobutanolamine; l-amino-2,3-propanediol; organic substituted ammonium radicals, which may be 2-amino-1,3-propanediol; diglycerolamine; 2-amino-2- the same or different organic substituted ammonium radimethyl-1,3-propanediol; 2-amino-2-n-propyl-1,3-propanecals; or the said salt may be a half alkali metal and half diol; and 2-amino-2-isopropyl-1,3-propanediol. Of espeorganic substituted ammonium salt which is the case cial utility are, as indicated above, monoethanolamine and where M is an alkali metal and M is an organic sub- 1 monoisopropanolamine. stituted ammonium radical. Of particular utility, as the l The polycarboxylic acids, the sulfo-derivatives of first ingredient, are the organic substituted ammonium which are employed in the preparation of the (a) ingredi-salts and the half ammonium half organic substituted dient, can be chosen from a large group, typical or illusammonium salt of the sulfosuccinic acid ester of the oleic trative examples of which are maleic acid, fumaric acid, acid amide of isopropanolamine, wherein the organic tartaric acid, glutaconic acid, itaconic acid, adipic acid, substituted ammonium radical is an alkyl amine containphthalic acid, sebacic acid, tricarballylic acid, and glutaric ing from 1 to 6 carbon atoms, especially isopropylamiuc. acid. Of particular utility are the aliphatic sulfopoly- In the case of the sulfotricarboxylic acid ester derivacarboxylic acids, especially the water-soluble sulfoditives, the said salt may be the organic substituted amcarboxylic acids containing from 4 to 8 carbon atoms. monium tri-salt, that is, where both M and M are i The sulfosuccinic acid derivatives are particularly preorganic substituted ammonium radicals, which maybe the ferred. same or different organic substituted ammonium radicals;

The salt-forming radicals represented by M or M or the said salt may be a one-third alkali metal and twocomprise, in the case of M, alkali metals (which term thirds organic substituted ammonium salt, in which case is h r used to n di m, p m, lithium and M is an organic substituted ammonium radical and M is ammonium); and, in the case of M and M, organic suban alkali metal; or vice versa, that is, said salt may be stituted ammonium radicals. The latter, which most atwo-thirds alkali metal and one-third organic substituted advantageously are water-soluble lower molecular weight ammonium salt, in which case M is an alkali metal and amines, may be selected from a wide group, typical ex- M is an organic substituted ammonium radical. amples of which are dimethylamine; diethylamine; tri- Illustrative examples of said (a) ingredient are the fole hy a n p opylam e; noi pr py n diisolowing (which include, also, the isomers thereofl Half ammonium half isopropylamine salt of the sulfosuqcluic acid ester of the oleic acid amide of isopropanolamzne Isopropyl amine dl-salt of the sult'osuccinie acid ester of the oleic acid amide of isopropanolamine Half sodium half butyl amine salt of the sulfosuccinic acid ester of the lauric acid amide of isopropanolamlne CHr-CH:

Half lithium half propyl amine salt of the sulfosucclnic acid ester of the olelc acid amide or monoethanolamrne Half sodium half isopropylamlne salt 01' the sulfosuccinlc acid ester of the oleic acid amide of isopropanolamine Half ammonium half isopropylamine salt of the sulfosuccinic acid ester of the oleic acid amide of isopropanolamine SO :Na

Halt sodium 'half butyl amine salt of the sulfosuccinic acid ester of the lauric acid amide of isopropauolamine Half ammonium half cyclohexylamlne salt of the sulfosuccinic acid ester of the myristic acid amide 0t isopropanolamine CH -CH;

CH -CH Half ammonium half isopropylamine salt of the sulfosuccinic acid ester of the palmitic acid amide otmonoethanolamine CH! SOaNa Halt sodium half isopropylamine salt of the sulfosuccinic acid ester of the oleic acid amide of isopropanolamiue Two-thirds ammonium one-third isopropylamine salt of the sulfotricarballylic acid ester of the oleic acide amide of isopropanolamine CnHaa-C O-NH-CHr-CHg-O C O NHIO O 0 acid ester of the oleic acid amide of monoethanolamine CuHar-O ONH-(CH2) a-CHa-O C O-GH-CHz-O O ONa Half sodium half propyl amine salt of the sulfosuccinic acid ester of the palmitic acid amide of butanolamine The (a) ingredient, for instance, the half alkali metal half amine salts of the sulfosuccinic acid esters of the higher fatty acid amides of monoethanolamine or isopropanolamine, can readily be made by reacting the higher fatty acid amide of monoethanolamine or isopropanolamine with maleic anhydride and heating to about 100 degrees C. to produce the maleic ester. The free carboxyl group of the maleic acid radical of said ester is then neutralized with an alkali metal or amine, and then the resulting compound is reacted with an alkali metal or amine bisulfite, as the case may be, in an aqueous or aqueous alcohol medium at 60 to 85 degrees C. The desired final product may be recovered and purified for use in the practice of my present invention although purification steps usually will not be necessary. The water content of said product, as used in the practice of my invention, should not exceed about SO;H.HNCH=(OH:):

Half ammonium half ls'opropylamine salt of the sultophthalic and, more advantageously, should be about 15% or less. It will be most convenient to introduce the sulfonic group into the molecule by the use of an alkali metal bisulfite, in which case the prior neutralization of the free carboxyl group of the maleic acid radical of the maleic ester will first have been carried out with the organic substituted ammonium base if a half alkali metal half organic substituted ammonium salt is to be prepared. It is not material to the success of my invention which of the M or the M' cation is an organic substituted ammonium radical but, as stated above, one of them should be an alkali metal and the other should be an organic substituted ammonium radical, or, in the broader aspect of my invention as I have shown, both M and M can be an organic substituted ammonium base cation. An alternative procedure involves neutralizing an alkali metal bisulfite with an amine and then the amine neutralized alkali metal bisulfite in the reaction with the maleic acid ester of the higher fatty acid amide of the monoethanolamine or isopropanolamine. In the formulae given above and in the claims for the (a) ingredient, it will be understood that the M and M may be interchanged, that is, the M cation may be attached to the S radical and the M cation may be attached to the free carboxyl group of the maleic acid radical, and the claims should be so read. It will be understood that the method of making the aforementioned salts of the sulfosuccinic acid esters of the higher fatty acid amides of monoethanolamine and isopropanolamine forms no part of the present invention and various methods for the production of said compounds will readily suggest themselves to those skilled in the art.

The second of said ingredients, which may, for convenience, be called the (b) ingredient, is an amine salt of an alkyl benzene sulfonic acid in which the alkyl radical contains from 12 to 18 carbon atoms. The alkyl radical, which is advantageously predominately a single higher alkyl radical, may be derived from polypropylenes, kerosene fractions, or the like, contains predominately from 12 to 18 carbon atoms, and, especially, predominately from 12 to 15 carbon atoms. The benzene nucleus may also contain lower alkyl substituents, provided that the number of carbon atoms in such lower alkyl constituents is in the range of from 1 to 3 and the number of such lower alkyl substituents does not exceed 2. The number of sulfonic acid radicals in the benzene nucleus maybe 1 or 2, but, especially, there is only approximately one sulfonic acid radical in the benzene nucleus.

Certain of the higher alkyl benzene sulfonic acids which, in the form of their organic amine salts, are employed as the (b) ingredient in the practice of my invention can be represented by the formula where R is a lower alkyl radical containing from 1 to 3 carbon atoms, such as methyl, ethyl, propyl and isopropyl, R is a higher alkyl radical containing from 12 to 18 carbon atoms and especially from 12 to 15 carbon atoms, n is zero to 2, and X is an organic amine cation.

Typical examples of the organic amines whose salts of the higher alkyl benzene sulfonic acids are employed as the (b) ingredient in accordance with my present invention are those which have been mentioned above as being representative of M in the general formula for the (a) ingredient. Particularly preferred are the alkyl amines containing from 1 to 6 carbon atoms and especially preferred is isopropyl amine. Typical or illustrative examples of the organic amine salts of the higher alkyl benzene sulfonic acids the use of which is encompassed by my invention are the following: diisopropanolamine salt of dodecyl benzene mono-sulfonic acid; isopropylamine salt of dodecyl benzene mono-sulfonic acid; diisopropylamine salt of dodecyl toluene mono-sulfonic acid; furfurylarnine salt of pentadecyl benzene mono-sulfonic acid; cyclonexylamine salt of dodecyl mono-sulfonic acid; diisopropylamine salt of dodecyl isopropyl benzene sultonic acid; morpholine salt of octadecyl benzene monosulfonic acid; and triisopropylamine salt of octadecyl benzene di-sulfonic acid; and mixtures of two or more thereof. The isopropylamine salt of dodecyl benzene monosulfonic acid is unusually satisfactory as the (b) ingredient and its use, in the combinations here involved, represents an important, though limited, embodiment of my invention.

It will be understood, of course, that mixtures of any two or more of the (a) and any two or more of the (b) ingredients can be employed in the practice of my present invention.

The biocidal toxicants which are used in accordance with my present invention and which, as stated above,

comprise insecticides and soil fumigants, may be selected from a wide group typical examples of which are fAldrin" (l,2,3',4,l0,10 -hexachloro 1,4,4a,5,8,'8a-'hexahydro-l, 4,5, 8dimethanonaphthalene); Dieldrin (1,2,3,4,10,l0- :hexachloro-QI-epoxy-1,4,4a,5,6,7,8,8a .octahydroxy l, 4-endo-exo-SgS-dimethanonaphthalene); Lindane (gamma isomer of benzene hexachloride); Heptachlor (1,-4, 5,6,7,8,8 hcptachloro 3a,4,7,7a tetrahydro 4,7-endomethanoindene); Nemagon" (l,2-dibr0mo-3-chloropropane); ethylene dibrornide; DDT; organic thiocyanates such as B-butoxy, B thiocyanodiethyl ether, bornyl thiocyanoacetate; trichlorobenzene; propyl, butyl, and amyl others of pentachlorophenol, and the like, and compatible mixtures of any two or more thereof. Of especial importance are Aldrin," Dieldrin," Lindane, Heptac'hlor, .and iNemagon" The organic solvent which is utilized in the preparation of the biocidal toxicant concentrates of my present invention,.and in-which the biocidal .toxicant is soluble,.-may be selected from aknown group of such organic solvents. Such organic solvents are of the type which are insoluble in the aqueous phase and, rat leastin most cases, will be per se insoluble in water. For convenience, said organic usolventsyarereterred to herein as being water-insoluble,

and the same is true of the biocidal toxicants, although the criterion is essential insolubility in the aqueous phase of the emulsion. These include, for instance, aromatic hydrocarbon solvents, or blends thereof with parafiinic or naphthenic solvents. Examples of: such solvents are kerosene; light refined mineral oil; rnethylnaphthalenes such as monomethyl naphthalene, dimethyl naphthalene and .trimethyl ;-naphthale ne; ethyl naphthalene; 2-rnethylpentanediol-1,2; dipropylene glycol methyl ethers; ben zene, toluene, aromatic naphthas, xylene, tetrahydronaphthalene, cyclohexane, and the like. These and various other organic solvents are frequently sold under trade names, such as Cyclosol 53, which is an aromatic petroleum fraction comprising ,methylated napththalenes; and Sovacide 544C which is an aromatic petroleumoil containing methylated naphthalenes.

The (a) and (b) ingredients are incorporated into solutions of the biocidal toxicants in the selected organic solvent or mixtures of organic solvents to produce biocidal toxicant concentrates. Typical of such biocidal toxicant concentrates are so-called concentrates containing, for instance, 2 pounds Heptachlor per gallon; 1.5 pounds Dieldrin per gallon; 1 pound gamma equivalent benzene hexachloride per gallon; and 45% Nemagon concentrates. The'content of the total of the (a) and (b) ingredients, by weight ofthe biocidal toxicant concentrate, will fall within the range of 3 to 30%, but, ordinarily, from 610 15%, and, particularly, from 8 to 12%, -.will be found quite satisfactory for most purposes. The relative proportions of the (a) and (b) ingredients, .or, in other words, the weight ratio of the (a) to the (b) ingredient, should be at least 2 to l, and is usually in the rangeof about 2to about 20, preferably on an average of about 4 to 10, parts of the (a) ingredient to 1 part of the (b) ingredient. The upper limit of the (a) ingredient may, if desired, be at least several times the values recited above. Within the limits stated, the proportions of ingredients may be varied in order to obtain optimum results in connection with any particular liquid fertilizer solution.

The 'liquid fertilizer solutions (with which the hereinabove described biocidal toxicant concentrates are admixed to form homogeneous emulsions or dispersions which are usable over periods of at least several hours) are, per se, well known in the art. They comprise aqueous solutions, usually strong or concentrated aqueous solutions even up to saturation, of Water-soluble compounds ,which fall into the category of providing at least .one of the elements potassium, nitrogen and phosphorus, including, among others, as previously pointed out, potassium chloride, potassium nitrate, potassium sulphate, ammonium nitrate, ammonium sulphate, ammonium phosphate, aqueous ammonia, and the like, as Well as organic water-soluble fertilizer materials particularly in conjunction with the inorganic water-soluble'salts, such as those mentioned above, an especially preferred example of such organic water-soluble fertilizer material being urea. The liquid fertilizers, which will normally include one or more of the aforementioned materials, may be standardized as to their nitrogen, phosphorus (as P and potassium (as K 0) contents. Typical examples of liquid fertilizer solutions, which can be used in conjunction with the novel biocidal toxicant concentrates of my invention are shown in a bulletin entitled Preparation Of Liquid Fertilizers, second edition, published by Victor Chemical Works, Chicago, Illinois.

Thefollowing examples are illustrative of biocidal toxi cant concentrates, and dispersant compositions for use therein, falling within the scope of my invention. Other specific embodiments will readily occur to those skilled in the art in the light of the guiding teachings and principles disclosed herein. All parts listed are by weight.

Example A Parts Aldrin (90%) 27.6 Kerosene (deodorized) 32 Cyclosol 53 (organic solvent) 30.4

Half ammonium half isopropylamine salt of the sulfosuccinic acid ester of the oleic acid amide of isopropanolamine 1 8 Isopropylamine salt of dodecyl benzene sulfonic acid 2 Example B Dieldrin (99%) 18.2 Heavy aromatic naphtha 71.8 Half ammonium half butylamine salt of the sulfosuccinic acid ester of the oleic acid amide of isopropanolamine 7 isopropylamine salt of dodecyl benzene sulfonic acid 3 Example C Benzene hexachloride (40% gamma isomer) 30 Xylene 60 Isopropylamine di-salt of the sulfosuccinic acid ester of the oleic acid amide of isopropanolamine 9 Cyclohexylarnine salt of pentadecyl benzene sulfonic acid 1 Example D Nemagon 45 Xylene 45 Half ammonium half isopropylamine salt of the sulfosuccinic acid ester of the oleic acid amide of isopropanolamine 8 10 Example G Parts Aldrin 25.0 Kerosene 33.0 Aromatic hydrocarbon solvent 34.5

Aminoethylethanolamine di-salt of the sulfosuccinic acid ester of the oleic acid amide of isopropanolamine 6.0 Aminoethylethanolamine salt of dodecyl benzene sulfonic acid 1.5

Example H Nemagon 45 Xylene 45 Isopropylamine tri-salt of the sulfotricarballylic acid ester of the oleic acid amide of isopropanolamine 8 Isopropylamine salt of dodecyl benzene sulfonic acid 2 Example I Benzene hexachloride (40% gamma isomer) Xylene Isopropylamine di-salt of the sulfophthalic acid ester of the oleic acid amide of monoethanolamine 9 Isopropylamine salt of pentadecyl benzene sulfonic acid 1 Example 1 Half ammonium half isopropylamine salt of the sulfosuccinic acid ester of the oleic acid amide of isopropanolamine 4 Isopropylamine salt of dodecyl benzene sulfonic acid 1 Example K Isopropylamine di-salt of the sulfosuccinic acid ester of the oleic acid amide of isopropanolamine 5 Isopropylamine salt of dodecyl benzene sulfonic acid 1 Kerosene 1.5 Cyclosol 53 (organicsolvent) 15 Example L Half sodium half cyclohexylamine salt of the sulfosuccinic acid ester of the oleic acid amide of monoethanolamine 7 Cyclohexylamine salt of dodecyl toluene sulfonic In the use of the biocidal toxicant concentrates of my present invention, it will be understood, of course, that the amount of the liquid fertilizer solution will be many times the amount of the biocidal toxicant concentrate. In

other words, the aqueous phase of the emulsion will, in all cases, be present in large excess over the oleaginous phase present in the biocidaltoxicant concentrate. While such excess may vary somewhat, inthe usualcase it will 11 be in the range of about 25 or. 30 to 60 or even more times that of the oleaginous phase, but will usually be from about 30 to 40 times that of the oleaginous phase, all in terms of parts by weight.

1n the use of the biocidaltoxicant concentrates of my invention, the same are simply admixed with the aqueous or liquid fertilizer solution, with suitable agitation. For instance, 2.5 parts of the toxicant concentrate of Example A are admixed, with stirring, with 9.7.5 pa ts. of a liquid fertilizer solution made up of 40 parts of 24.3% aqueous ammonia, 45.87 parts of 75% phosphoric acid, and 14.13 parts of water, all of said parts being by weight. in another typical example, 3 parts of the toxicant concentrate of Example B are admixed with 97 parts of said liquid fertilizer solution. Again, 3.3 parts of the toxicant concentrate of Example H are admixed with 96.7 parts of a liquid fertilizer solution made up of 44.3, parts ammonium nitrate, 35.4 parts urea, and 20.3 parts of water. Other illustrative commercial types of liquid fertilizer sol t ons w t whic my n l b dal x ca onc ntra c n e u ed a e the $91 l 8-2. .0, (der e from on um pho phate); 88.8. (de e v i amm um. p p ate, p t ss m h de. ure Ut 32 (de e f om. mmon u tr t nd u a), nd l 0 (deri ed f om ammonium n iospha sau u ea)- This application is a continuation-in-part of my prior application Serial No. 554,643, filed December 22, 1955, now abandoned.

What I claim as new and desire to protect by Letters Patent of the United States is:

1. A dispersant composition, soluble in organic solvent solutions of water-insoluble biocidal toxicants, comprising (a) a compound in the form of an alcohol nontertiary amine, a reactive hydrogen of an amine group of said amine being replaced by a fatty acid acyl radical containing from 8 to 18 carbon atoms, and a reactive hydrogen of a hydroxy group of said amine being replaced by an acyl radical of a sulfopolycarboxylic acyl radical, said latter acyl radical containing from 4 to 8 carbon atoms and being represented by the formula wherein Y is the completely decarboxylated residue of a polycarboxylic acid, M is a member of the group consisting of alkali metals and organic substituted ammonium radicals, M is an organic substituted ammonium radical, and n is an integer from l to 2, and (b) an amine salt of an alkyl benzene sulfonic acid in which the alkyl rad c l contains m .2 to .8 a bon stem e weight ratio of said (a) to said (I ingredient being at least 2 to 1.

2. A dispersant composition, soluble in organic sol vent solutions of water-insoluble biocidal toxicants, comprising (a) a compound corresponding to the formula wherein R-CO- is a fatty acid acyl radical containing from 12 to 18 carbon atoms, X is the completely deaminatcd and dehydroxylated residue of water-soluble alcohol primary amine, Y is the completely decarboxylated residue of a water-soluble polycarboxylic acid containing from 4 to 8 carbon atoms, M is a member selected from the group consisting of alkali metals and lower organic substituted ammonium radicals, M"is a lower organic substituted ammonium radical, and n is an integer from i to 2, and (b) an amine salt of an alkyl benzene sulfonic acid in which the alkyl radical contains from 12 to 18 carbon atoms, the weight ratio of said (a) to said (b) ingredient being at least 2 to 1.

3. A dispersant composition in accordance with claim 2, wherein M and M are alkyl ammonium containing from 1 to 6 carbon atoms, and the amine salt of the alkyl benzene sulfonic acid is an alkyl amine containing from 1 to 6 carbon atoms.

4. A dispersant composition in accordance with claim 2, wherein M is ammonium and M is isopropyl ammonium, and the amine salt of the alkyl benzene sulfonic acid is isopropylamine.

5. A dispersant composition in accordance with claim 2, wherein M is ammonium, M is cyclohexyl ammonium, and the amine salt of the alkyl benzene sulfonic acid is cyclohexylamine.

6. A toxicant concentrate. comprising an organic solvent solution of an organic water-insoluble biocidal toxicant and containing, dissolved therein, (a) a compound in the form of an alcohol non-tertiary amine a reactive hydrogen of an amino group of said amine being replaced by, a fatty acid acyl radical containing from 8 to 18 carbon atoms, and a reactive hydrogen of an hydroxy group of said amine being replaced by an acyl radical of a sulfopolycarboxylic acyl radical, containing from 4 to 8 carbon atoms and said latter acyl radical being represented by the formula wherein Y is the completely decarboxylated residue of a polycarboxylic acid, M is a member of the group consisting of alkali metals and organic substituted ammonium radicals, M is an organic substituted ammonium radical, and n is an integer from 1 to 2, and (b) an organic substituted ammonium radical salt of an alkyl benzene sulfonic acid in which the alkyl radical contains from 12 to 18 carbon atoms, the weight ratio of said (a) to said (b) ingredient being at least 2 to 1, the total of said (a) and (b) ingredients constituting from 3 to 30%, by weight, of said concentrate, said concentrate being adapted, upon admixture with aqueous solutions containing upwards of 20% of fertilizer ingredients, to form a homogeneous dispersion usable for periods ot the order of at least several hours.

7. A toxicant concentrate comprising an organic solvent solution of an organic water-insoluble biocidal toxicant and containing, dissolved therein, (a) a compound corresponding to the formula R,o0-NHx -oo0Y -cooi\ soiMj wherein RwCOfi, is a fatty acid acyl radical containing from 12 to, 18 carbon atoms, X is the. completely deaminated and dehydroxylated residue of a watersoluble alcohol primary amine, Y is the completely decarboxylated residue of a water-soluble polycarboxylic acid containing from 4 to 8 carbon atoms, M is a member selected from the group consisting of alkali metals and lower organic substituted ammonium radicals, M is a lower organic substituted ammonium radical, and r1 is an integer from 1 to 2, and (b) an amine salt of an alkyl benzene sulfonic acid in which the alkyl radical contains from 1-2 to 18 carbon atoms, the weight ratioof said (a) to said (b) ingredient being at least 2 to 1.

8. A toxicant concentrate. in accordance with claim 7, wherein M and M are alkyl ammonium containing from 1 to 6 carbon atoms, the amine salt of the alkyl benzene sulfonic acid is an alkyl amine containing from 1 to. 6- carbon atoms, and wherein the total of said. ta). and (b) ingredients constitutes from 6 to 15% by weight, of said concentrate. I

9. A toxicant concentrate in accordance with claim 7, wherein M is ammonium and M. is isopropyl ammonium, wherein the amine salt of the alkyl benzene sulfonic acid is isopropylamine, and wherein the total of said (a) and. (b) ingredients constitutes from 6 to 15%, by weight, of said concentrate.

10. A toxicant concentrate in accordance with claim 7, wherein M is ammonium and M' is cyclohexyl ammonium, wherein the aminesalt of the alkyl benzene sulfonic acid is cyclohexylamine, and wherein the total of said 13 (a) and (b) ingredients constitutes from 6 to 15%, by weight, of said concentrate.

11. The composition of claim 6, wherein the biocidal toxicant is at least one member selected from the group consisting of 1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro- 1,4,5 ,S-dimethanonaphthalene; 1,2,3,4,10,10-hexachloro-6,7-epoxy, 1,4,4a,5,6,7,8,8a-octahydroxy-1,4-endoeXo-S,S-dimethanonaphthalene; gamma isomer of benzene hexachloride; 1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-endo-methanoindene; and 1,2-dibromo-3-chloropropane.

12. The compositionof claim 7, wherein the biocidal toxicant is at least one member selected from the group consisting of 1,2,3,4,l0,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4,5,S-dimethanonaphthalene; 1,2,3 ,4,10,10-hexachlor-6,7-epoxy, 1,4,4a,5,6,7,8,8a-octahydroxy-1,4-endoexo-S,S-dimethanonaphthalene; gamma isomer of benzene hexachloride; 1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-endo-methanoindene; and 1,2-dibromo-3-chloropropane.

13. A combination biocidal toxicant-water soluble inorganic salt fertilizer composition containing an aqueous phase comprising a water solution of said water-soluble inorganic salt fertilizer material, and a normally waterimmiscible oleaginous phase comprising an organic solvent solution of said biocidal toxicant, said composition comprising a substantially homogeneous emulsion which includes, in admixture therewith, (a) a compound in the form of an alcohol non-tertiary amine a reactive hydrogen of an amino group of said amine being replaced by a fatty acid acyl radical containing from 8 to 18 carbon atoms, and a reactive hydrogen of an hydroxy group of said amine being replaced by an acyl radical of a sulfopolycarboxylic acyl radical, said latter acyl radical containing from 4 to 8 carbon atoms and being represented by the formula a 1 o C'Y(GOOM),,

wherein Y is the completely decarboxylated residue of a .polycarboxylic acid, M is a member of the group consisting of alkali metals and organic substituted ammonium radicals, M is an organic substituted ammonium. radical, and n is an integer from 1 to 2, and (b) an organic substituted ammonium radical salt of an alkyl benzene sulfonic acid in which the alkyl radical contains from 12 to 18 carbon atoms, the weight ratio of said (a) to said (b) ingredient being at least 2 to 1, the total of said (a) and (b) ingredients constituting from 3 to 30%, by weight, of the water-immiscible oleaginous phase.

14. A combination biocidal toxicant-water soluble inorganic salt fertilizer composition containing an aqueous phase comprising a water solution of said water-soluble inorganic salt fertilizer material, and a normally waterimmiscible oleaginous phase comprising an organic solvent solution of said biocidal toxicant, said composition comprising a substantially homogeneous emulsion which includes, in admixture therewith, (a) a compound corresponding to the formula wherein RCO is a fatty acid acyl radical containing from 12 to 18 carbon atoms, X is the completely deaminated and dehydroxylated residue of water-soluble alcohol primary amine, Y is the completely decarboxylated residue of a water-soluble polycarboxylic acid containing from 4 to 8 carbon atoms, M is a member selected from the group consisting of alkali metals and lower organic substituted ammonium radicals, M is a lower organic sub- "stituted ammonium radical, and ,n is an integer from 1 to 2, and (b) an amine salt of an alkyl benzene, sul- 'fonic acid in which the alkyl radical contains from 12 to ,18 carbon atoms, the weight ratio of said (a) to said (b) V ingredient being at least 2 to 1, the total of said (a) and (b) ingredients constituting from 3 to 30%, by weight,

of the water-immiscible oleaginous phase.

15. A toxicant concentrate comprising an organicsolvent solution of an organic water-insoluble biocidal toxicant and containing, dissolved therein, (a) a compound corresponding to the formula wherein RCO is an acyl radical containing from 12 to 18 carbon atoms, X is the completely deaminated and dehydroxylated residue of a member selected from the group consisting of monoethanolamine and monoisopropanolamine, M is a member selected from the group consisting of alkali metals and organic substituted ammonium radicals, and M is an organic substituted ammonium radical, and (b) an amine salt of an alkyl benzene sulfonic acid in which the alkyl radical contains from 12 to 18 carbon atoms, the weight ratio of said (a) to said (b) ingredient being at least 2 to 1, the total of said (a) and (b) ingredients constituting from 3 to 30%, by weight, of said concentrate, said concentrate being adapted, upon admixture with aqueous solutions containing upwards of 20% of water-soluble inorganic salt fertilizer ingredients, to form a homogeneous dispersion usable for periods of the order of at least several hours.

16. A toxicant concentrate in accordance with claim 15, wherein M and M are alkyl ammonium containing from 1 to 6 carbon atoms, the amine salt of the alkyl benzene sulfonic acid is an alkyl amine containing from 1 to 6 carbon atoms, and wherein the total of said (a) and (b) ingredients constitutes from 6 to 15%, by weight, of said concentrate.

17. A toxicant concentrate comprising an organic solvent solution of an organic water-insoluble biocidal toxicant and containing, dissolved therein, (a) a compound corresponding to the formula wherein RCO is an acyl radical containing from 12 to 18 carbon atoms, X is the completely deaminated and dehydroxylated residue 'of a member selected from the :group consisting of monoethanolarnine and monoisopropanolamine, M is a member selected from the group consisting ofalkali metals and organic substituted ammonium radicals, and M is alkyl ammonium, and (b) an alkyl amine salt of an alkyl benzene sulfonic acid corresponding to the formula (Rh SOaX where R is a lower alkyl radical containing from 1 to 3 carbon atoms, R is a higher alkyl radical containing from 12 to 18 carbon atoms, n is zero to 2, and X is an organic amine cation, the weight ratio of said (a) to said (b) ingredient being at least 2 to 1, the total of said (a) and (b) ingredients constituting from 3 to 30%, by weight,

' of said concentrate, said concentrate being adapted, upon admixture with aqueous solutions containing upwards of 20% of water-soluble inorganic salt fertilizer ingredients, to form a homogeneous dispersion usable for periods. of the order of at least several hours.

18. A toxicant concentrate comprising an organic solvent solution of an organic water-insoluble biocidal. toxicant and containing, dissolved therein, (a) an organic substituted ammonium di-salt of the sulfosuccinic acid ester of a fatty acid amide of monoisopropanolamine the fatty acid radical of which contains from 12 to 18 carbon atoms, and (b) an amine salt of dodecyl benzene sulfonic acid, the weight ratio of said (a) to said (b) ingredient being at least 2 to l, and the total of said (a) and (b) ingredients constituting from 6 to 15%, by weight, of said concentrate, said concentrate being adapted, upon 15 admixture with aqueous solutions containing upwards of 20% of water-soluble inorganic salt fertilizer ingredients, to form a homogeneous dispersion usable for periods of the order of at least several hours.

19. A toxicant concentrate comprising an organic solvent solution of an organic water-insoluble biocidal toxicant and containing, dissolved therein, (a) a compound corresponding to the formula wherein M and M are dissimilar and are selected from the group consisting of ammonium and isopropyl ammonium, and (b) the isopropyl amine salt of dodecyl benzene sulfonic acid, the Weight ratio of said (a) to said (b) ingredient being from about 2 to about 20 of (a) to 1 of (b), the total of said (a) and (b) ingredients constituting from 6 to 15%, by weight, of said concentrate, said concentrate being adapted, upon admixture with aqueous solutions containing upwards of 20% of watersoluble inorganic salt fertilizer ingredients, to form a homogeneous dispersion usable for periods of the order ofat least several hours.

20. A toxicant concentrate comprising an organic solvent solution of an organic water-insoluble biocidal toxicant and containing, dissolved therein, (a) a compound corresponding to the formula CH G msoNH-oHg iH-0c0-crt-cH .-qo OM wherein M and M are dissimilar and are selected from the group consisting of alkali metals and alkyl ammonium, and (b) an alkyl amine salt of dodecyl benzene sulfonic acid, the weight ratio of said (a) to said (b) ingredient being from about 2 to 20 of (a) to 1 of (b), the total of said (a) and (b) ingredients constituting from 6 to 15%, by weight, of said concentrate, said concentrate being adapted, upon admixture with aqueous solutions containing upwards of 20% of water-soluble inorganic salt fertilizer ingredients to form a homogeneous dispersion usable for periods of the order of at least several hours.

21. A dispersant composition, soluble in organic solvent solutions of water-insoluble biocidal toxicants, comprising (a) a compound corresponding to the formula wherein RCO- is an acyl radical containing from 12 to 18 carbon atoms, X is the completely deaminated and dehydroxylated residue of a member selected from the group consisting of monoethanolamine and monoisoprop'anolamine, M is a member selected from the group consisting of alkali metals and organic substituted ammonium radicals, and M is an organic substituted ammonium radical, and (b) an amine salt of an alkyl b'enzenesulfonic acid in which the alkyl radical contains from 12 to 18 carbon atoms, the weight ratio of said (a) to said (b) ingredient being at least 2 to 1.

22. A dispersant composition in accordance with claim 21, wherein M and M are alkyl ammonium containing from 1 to 6 carbon atoms, and the amine salt of the alkyl benzene sulfonic acid is an alkyl amine containing from 1 to 6 carbon atoms.

23. A dispersant composition, soluble in organic solvent solutions of organic water-insoluble'biocidal toxicants comprising (a) a compound corresponding to the formula S Oaiu' I wherein R--CO- is an acyl radical containing from 12 to 18 carbon atoms, X is the completely dearninatedand dehydroxylated residue of a member selected from the group consisting of monoethanolamine and monoisopropanolamine, M is a member selected from the group consisting of alkali metals and organic substituted ammonium radicals, and M is alkyl ammonium, and (b) an alkyl amine salt of an alkyl benzene sulfonic acid corresponding to the formula (R)n SOaX where R is a lower alkyl radical containing from 1 to 3 carbon atoms, R is a higher alkyl radical containing from 12 to 18 carbon atoms, 11 is zero to 2, and X is an organic amine cation, the weight ratio of said (a) to said (b) ingredient being at least 2 to l.

24. A dispersant composition, soluble in organic solvent solutions of organic water-insoluble biocidal toxicants, comprising (a) an organic substituted ammonium di-salt of the sulfosuccinic acid ester of a fatty acid amide of monoisopropanolamine the fatty acid radical of which contains from 12 to 18 carbon atoms, and (b) an amine salt of dodecyl benzene sulfonic acid, the weight ratio of said (a) to said (b) ingredient being at least 2 to 1.

25. A dispersant composition, soluble in organic solvent solutions of organic water-insoluble biocidal toxicants, comprising (a) a compound corresponding to the formula wherein M and M' are dissimilar and are selected from the group consisting of alkali metals and alkyl ammonium, and (b) an alkyl amine salt of dodecyl benzene sulfonic acid, the alkyl amine radicals containing from 1 to 6 carbon atoms, the weight ratio of said (a) to said (b) ingredient being from about 2 to about 6 of (a) to 1 of 26. A dispersant composition, soluble in organic solvent solutions of organic water-insoluble biocidal toxicants, comprising (a) a compound corresponding to the formula wherein RCO is a fatty acid acyl radical containing from 12 to 18 carbon atoms, and M and M are dissimilar and are selected from the group consisting of alkali metals and isopropyl ammonium, and (b) the isopropyl amine salt of dodecyl benzene sulfonic acid, the weight ratio of said (a) to said (b) ingredient being from about 2 to 6 of (a) to 1 of (b).

27. A combination biocidal toxicant-water soluble inorganic salt fertilizer composition containing an aqueous phase comprising a water solution of said water-soluble inorganic salt fertilizer material, and a normally water-immiscible oleaginous phase comprising an organic solvent solution of said biocidal toxicant, said composition comprising a substantially homogeneous emulsion which includes, in admixture therewith, (a) a compound corresponding to the formula R-CO-NH-X-OCO-CH-CHz-COOM SOzM wherein R-CO-- is an acyl radical containing from 12 to 18 carbon atoms, X is the completely deaminated and dehydroxylated residue of a member selected from the group consisting of monoethanolamine and monoisopropanolamine, M is a member selected from the group consisting of alkali metals and organic substituted ammonium radicals, and M is an organic substituted ammonium radical, and (b) an amine salt of an alkyl benzene sulfonic acid in which the alkyl radical contains from 12 to 18 17 carbon atoms, the weight ratio of said (a) to said (b) ingredient being at least 2 to 1, the total of said (a) and (b) ingredients constituting from 3 to 30%, by weight, of the water-immiscible oleaginous phase.

References Cited in the file of this patent UNITED STATES PATENTS 2,236,528 Epstein et a1. Apr. 1, 1941 18 Y Epstein et a1 Apr. 1, 1941 Keenan Aug. 10, 1954 Fike Jan. 17, 1956 Searle July 24, 1956 OTHER REFERENCES Brown et al.: Soap, Formulations of Emulsions, July 1951, pp. 43, 45, 47 and 49. 

2. A DISPERSANT COMPOSITION, SOLUBLE IN ORGANIC SOLVENT SOLUTIONS OF WATER-INSOLUBLE BIOCIDAL TOXICANTS, COMPRISING (A) A COMPOUND CORRESPONDING TO THE FORMULA 